TWI635341B - Method of manufacturing liquid crystal display device - Google Patents

Method of manufacturing liquid crystal display device Download PDF

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TWI635341B
TWI635341B TW104139757A TW104139757A TWI635341B TW I635341 B TWI635341 B TW I635341B TW 104139757 A TW104139757 A TW 104139757A TW 104139757 A TW104139757 A TW 104139757A TW I635341 B TWI635341 B TW I635341B
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liquid crystal
crystal display
display device
film
photoreactive polymer
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TW201629601A (en
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淺木大明
三宅敢
川平雄一
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日商夏普股份有限公司
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Abstract

本發明提供一種可降低於光配向膜之配向處理中照射之光之量，且獲得良好之對比度及視角特性之液晶顯示裝置之製造方法。 The present invention provides a method of manufacturing a liquid crystal display device which can reduce the amount of light irradiated in the alignment treatment of the photoalignment film and obtain good contrast and viewing angle characteristics.

本發明之液晶顯示裝置之製造方法係具備光配向膜之液晶顯示裝置之製造方法，且依序包括：步驟(1)，其於基板上形成含有2種以上之聚合物及溶劑之光配向膜材料之膜；步驟(2)，其對上述膜進行使上述溶劑蒸發之預焙燒；步驟(3)，其對預焙燒後之上述膜自低溫至高溫於複數個溫度下階段性地進行正式焙燒；及步驟(4)，其對正式焙燒後之上述膜進行偏光照射；並且上述2種以上之聚合物中之至少一者為側鏈具有光官能基之光反應性聚合物。 A method for producing a liquid crystal display device of the present invention is a method for producing a liquid crystal display device comprising a photo-alignment film, and the method includes the step (1) of forming a photo-alignment film containing two or more kinds of polymers and solvents on a substrate. a film of a material; a step (2) of pre-baking the film to evaporate the solvent; and a step (3) of periodically calcining the film after pre-baking from a low temperature to a high temperature at a plurality of temperatures And the step (4), wherein the film after the main baking is subjected to polarized light irradiation; and at least one of the two or more types of polymers is a photoreactive polymer having a photofunctional group in a side chain.

Description

液晶顯示裝置之製造方法 Method of manufacturing liquid crystal display device

本發明係關於一種液晶顯示裝置之製造方法。更詳細而言，關於一種 與配向膜之形成條件相關之液晶顯示裝置之製造方法。 The present invention relates to a method of fabricating a liquid crystal display device. In more detail, about one kind A method of manufacturing a liquid crystal display device related to conditions for forming an alignment film.

近年來，液晶顯示裝置等薄型顯示裝置快速普及，不僅是電視用途，亦廣泛用於電子書、相框、IA(Industrial Appliance：產業機器)、PC(Personal Computer：個人電腦)、平板PC、智慧型手機用途等。 In recent years, thin display devices such as liquid crystal display devices have rapidly spread, not only for television applications, but also widely used in e-books, photo frames, IA (Industrial Appliances), PCs (Personal Computers), tablet PCs, and smart phones. Mobile phone usage, etc.

於液晶顯示裝置中，要求使液晶分子均一地配向，作為用以使液晶分子配向之配向膜之配向處理方法，例如可列舉摩擦法或光配向法，先前，廣泛採用藉由布摩擦配向膜之表面之摩擦法。然而，於使用摩擦法之情形時，因布之發塵所引起之異物不良及顯示不均、以及因藉由布進行摩擦時之靜電所引起之薄膜電晶體元件之破壞等成為問題。又，隨著平板PC、智慧型手機等之高精細化發展，於因布之毛之密度而限制配向處理精度之摩擦法中，逐漸難以使液晶分子均一地配向。因此，為了解決該等問題，近年來研究藉由照射紫外線等光而對配向膜賦予各向異性，使之產生配向限制力之光配向法，以代替摩擦法。 In the liquid crystal display device, it is required to uniformly align the liquid crystal molecules, and as an alignment treatment method for the alignment film for aligning the liquid crystal molecules, for example, a rubbing method or a photo-alignment method may be mentioned. Previously, the surface of the alignment film was rubbed by the cloth. The friction method. However, in the case of using the rubbing method, the foreign matter caused by the dust of the cloth is poor and the display is uneven, and the destruction of the thin film transistor element due to the static electricity when rubbed by the cloth becomes a problem. Further, with the development of high-definition of flat-panel PCs and smart phones, it is difficult to uniformly align liquid crystal molecules in the rubbing method in which the precision of alignment processing is limited by the density of the cloth. Therefore, in order to solve such problems, in recent years, a photo-alignment method in which anisotropy is imparted to an alignment film by irradiation of light such as ultraviolet rays to cause an alignment restricting force has been studied instead of the rubbing method.

於光配向法中，通常按照配向膜材料之塗佈、預焙燒、正式焙燒、偏光照射之順序而形成配向膜。對配向膜材料亦進行各種研究，例如，於專利文 獻1中，研究包含材料選擇之自由度較高之光反應性化合物之光配向膜用組合物。 In the photo-alignment method, an alignment film is usually formed in the order of coating, pre-baking, main baking, and polarized light irradiation of an alignment film material. Various studies have also been conducted on alignment film materials, for example, in patent literature. In the first embodiment, a composition for a photo-alignment film containing a photoreactive compound having a high degree of freedom in material selection was examined.

又，近年來研究藉由於形成配向膜之過程中進行正式焙燒，而提高高分子(聚合物)之配向秩序。例如，於非專利文獻1中揭示有將主鏈包含偶氮苯之聚醯胺酸塗佈於基板上，照射直線偏光紫外線，然後進行正式焙燒，測定所獲得之聚醯亞胺配向膜之配向秩序，結果正式焙燒後之配向秩序高於正式焙燒前之配向秩序。又，於專利文獻2中，使用側鏈型高分子膜於基板上形成塗膜後，照射偏光之紫外線，繼而進行加熱，藉此實現對側鏈型高分子膜之高效率之各向異性之導入。 Further, in recent years, studies have been conducted to improve the alignment order of polymers (polymers) by performing main baking in the process of forming an alignment film. For example, Non-Patent Document 1 discloses that a polyamine containing azobenzene in a main chain is coated on a substrate, irradiated with a linearly polarized ultraviolet ray, and then subjected to a main baking, and the alignment of the obtained polyimide film is measured. Order, the result is that the order of orientation after formal roasting is higher than the order of orientation before formal roasting. Further, in Patent Document 2, a side chain type polymer film is used to form a coating film on a substrate, and then irradiated with polarized ultraviolet rays, followed by heating, thereby achieving high efficiency anisotropy of the side chain type polymer film. Import.

專利文獻1：國際公開第2012/093682號 Patent Document 1: International Publication No. 2012/093682 專利文獻2：國際公開第2013/081066號 Patent Document 2: International Publication No. 2013/081066

非專利文獻1：Sakamoto等(K.Sakamoto,et al)，「光配向之聚醯胺酸膜之面內分子秩序：熱醯亞胺化時之提昇(In-plane Molecular Order of a Photo-oriented Polyamic Acid Film：Enhancement upon Thermal Imidization)」，分子晶體及液晶(Molecular Crystals and Liquid Crystals)，美國，Taylor & Francis Inc., 2004, Vol.412, p.293-299 Non-Patent Document 1: Sakamoto et al. (K. Sakamoto, et al.), "In-plane Molecular Order of a Photo-oriented" in the in-plane molecular order of photo-aligned poly-proline membranes Polyamic Acid Film: Enhancement upon Thermal Imidization), Molecular Crystals and Liquid Crystals, USA, Taylor & Francis Inc., 2004, Vol. 412, p. 293-299

然而，於光配向法中存在如下問題：難以獲得充分之配向限制力，為了藉由光配向法獲得高於藉由摩擦法進行配向處理之製品之對比度，於光照射(例如偏光照射)中需要大量之能量(照射量)。例如，必需超過數百mJ/cm2之偏光照射量，多數情況下必需數J/cm2之照射量。若配向處理所需之偏光照射量 較大，則存在不僅處理時間增加，曝光裝置之劣化亦變早，構成液晶顯示裝置之基板之各種有機膜發生損傷等問題。又，存在視角特性不充分之問題。 However, in the photo-alignment method, there is a problem in that it is difficult to obtain a sufficient alignment restricting force, and in order to obtain a contrast higher than that of an article subjected to alignment treatment by a rubbing method by a photo-alignment method, it is required in light irradiation (for example, polarized light irradiation). A large amount of energy (irradiation). For example, it is necessary to exceed the amount of polarized light of several hundred mJ/cm2, and in many cases, an irradiation amount of several J/cm2 is necessary. The amount of polarized light required for alignment processing When the processing time is large, there is a problem that not only the processing time is increased, but also the deterioration of the exposure device is earlier, and various organic films constituting the substrate of the liquid crystal display device are damaged. Moreover, there is a problem that the viewing angle characteristics are insufficient.

上述專利文獻1記載之發明未對配向膜之焙燒製程詳細地進行揭示，就使正式焙燒之條件最佳化，進一步提高聚合物之配向秩序之方面而言，存在用以解決上述問題之功夫之餘地。 In the invention described in the above Patent Document 1, the baking process of the alignment film is not disclosed in detail, and the conditions for the main baking are optimized, and the alignment order of the polymer is further improved. room.

上述非專利文獻1對正式焙燒之條件僅揭示250℃、1小時，就使正式焙燒之條件最佳化之方面而言，存在用以解決上述問題之功夫之餘地。又，上述非專利文獻1對預焙燒亦未作任何揭示。於不進行預焙燒之情形時，產生光配向膜之膜厚不均，顯示品質降低。 In the above-mentioned Non-Patent Document 1, the conditions for the main baking are disclosed only at 250 ° C for 1 hour, and there is room for solving the above problems in terms of optimizing the conditions of the main baking. Further, the above non-patent document 1 does not disclose any pre-baking. When the pre-baking is not performed, the film thickness of the photo-alignment film is uneven, and the display quality is lowered.

於上述專利文獻2記載之發明中，視角特性仍不充分，為了解決上述問題，存在使配向膜之焙燒製程最佳化之餘地。 In the invention described in the above Patent Document 2, the viewing angle characteristics are still insufficient, and in order to solve the above problems, there is room for optimizing the baking process of the alignment film.

本發明係鑒於上述現狀而完成者，其目的在於提供一種可降低於光配向膜之配向處理中照射之光之量，且獲得良好之對比度及視角特性之液晶顯示裝置之製造方法。 The present invention has been made in view of the above circumstances, and an object of the invention is to provide a method of manufacturing a liquid crystal display device which can reduce the amount of light irradiated in the alignment treatment of a photoalignment film and obtain good contrast and viewing angle characteristics.

本發明者等人首先研究如非專利文獻1及專利文獻2般於光照射後進行正式焙燒之方法，作為於光配向法中降低光照射量之方法。根據該方法，由於可進行藉由正式焙燒提高構成光配向膜之聚合物之配向秩序之所謂自組裝，故而藉由降低之光照射量亦可獲得充分之配向限制力。然而，根據本發明者等人之研究可知，自組裝之光配向膜之相位差較大，使液晶顯示裝置之視角特性變差。 The inventors of the present invention first studied a method of performing main baking after light irradiation as in Non-Patent Document 1 and Patent Document 2, and as a method of reducing the amount of light irradiation in the photoalignment method. According to this method, since the so-called self-assembly of the alignment order of the polymer constituting the photo-alignment film can be performed by the main baking, a sufficient alignment regulating force can be obtained by reducing the amount of light irradiation. However, according to the study by the inventors of the present invention, the phase difference of the self-assembled photoalignment film is large, and the viewing angle characteristics of the liquid crystal display device are deteriorated.

因此，本發明者等人對光配向法中所需之偏光照射量變高之原因進行研究，著眼於使用混合有光反應性聚合物、非光反應性聚合物等2種以上之聚 合物之配向膜材料。而且，發現：配向膜中之光反應性聚合物與非光反應性聚合物之層分離不充分，藉此配向秩序難以提高，於正式焙燒步驟後之偏光照射步驟中必需較多之偏光照射。 Therefore, the inventors of the present invention have studied the cause of the increase in the amount of polarized light required for the photo-alignment method, and have focused on the use of two or more kinds of polymers such as a photoreactive polymer and a non-photoreactive polymer. Alignment film material. Further, it has been found that the separation of the layer of the photoreactive polymer and the non-photoreactive polymer in the alignment film is insufficient, whereby the alignment order is difficult to be improved, and more polarized light irradiation is required in the polarized light irradiation step after the main baking step.

對此，本發明者等人想到於進行正式焙燒之步驟中自低溫至高溫於複數個溫度下階段性地進行正式焙燒。而且，發現：藉由並非是單一溫度而是自低溫至高溫於複數個溫度下階段性地進行正式焙燒，可促進光反應性聚合物及非光反應性聚合物之層分離，使配向膜上層存在較多之光反應性聚合物，使配向膜下層存在較多之非光反應性聚合物。又，發現：藉由自低溫至高溫於複數個溫度下階段性地進行正式焙燒，可充分地去除配向膜材料中所包含之溶劑，即便於正式焙燒後進行偏光照射，構成配向膜之聚合物亦不會伴隨有自組裝，可使配向膜之相位差較小，其結果為可獲得良好之視角特性。 On the other hand, the inventors of the present invention thought that in the step of performing the main baking, the main baking is performed stepwise from a low temperature to a high temperature at a plurality of temperatures. Moreover, it has been found that by performing the main calcination stepwise at a plurality of temperatures from a low temperature to a high temperature instead of a single temperature, the layer separation of the photoreactive polymer and the non-photoreactive polymer can be promoted, and the upper layer of the alignment film can be promoted. There are many photoreactive polymers, and there are many non-photoreactive polymers in the lower layer of the alignment film. Further, it has been found that by performing the main calcination stepwise at a plurality of temperatures from a low temperature to a high temperature, the solvent contained in the alignment film material can be sufficiently removed, and even after the main calcination, the polarized light is irradiated to form a polymer of the alignment film. It is also not accompanied by self-assembly, and the phase difference of the alignment film can be made small, and as a result, good viewing angle characteristics can be obtained.

其次，本發明者等人著眼於光反應性聚合物之結構，發現藉由光反應性聚合物於側鏈具有光官能基，即便於正式焙燒後進行偏光照射，亦可藉由較少之偏光照射使聚合物側鏈進行再排列，對配向膜賦予單軸各向異性，且可將配向膜之相位差抑制為非常低。 Next, the present inventors focused on the structure of the photoreactive polymer and found that the photoreactive polymer has a photofunctional group in the side chain, and even if it is subjected to polarized light after the main baking, it can be made less polarized. Irradiation causes the polymer side chains to be rearranged to impart uniaxial anisotropy to the alignment film, and the phase difference of the alignment film can be suppressed to be extremely low.

根據以上情況，想到可巧妙地解決上述問題，從而達到本發明。 Based on the above, it is thought that the above problems can be solved skillfully to achieve the present invention.

即，本發明之一態樣可為液晶顯示裝置之製造方法，其係具備光配向膜之液晶顯示裝置之製造方法，且依序包括：步驟(1)，其於基板上形成含有2種以上之聚合物及溶劑之光配向膜材料之膜；步驟(2)，其對上述膜進行使上述溶劑蒸發之預焙燒；步驟(3)，其對預焙燒後之上述膜自低溫至高溫於複數個溫度下階段性地進行正式焙燒；及步驟(4)，其對正式焙燒後之上述膜進行偏光照射；並且上述2種以上之聚合物中之至少一者為側鏈具有光官能基之光反應性聚合物。 That is, one aspect of the present invention may be a method for producing a liquid crystal display device, which is a method for manufacturing a liquid crystal display device including a photo-alignment film, and includes, in order, step (1), which comprises two or more kinds on a substrate. a film of a photo-alignment film material of a polymer and a solvent; a step (2) of pre-baking the film to evaporate the solvent; and a step (3) of the film after pre-baking from a low temperature to a high temperature Formal calcination is carried out stepwise at a temperature; and step (4) is performed to polarize the film after the main calcination; and at least one of the above two or more polymers is a light having a photofunctional group in the side chain Reactive polymer.

根據本發明之一態樣，可提供一種可降低於光配向膜之配向處理中照射之光之量，且獲得良好之對比度及視角特性之液晶顯示裝置之製造方法。 According to an aspect of the present invention, it is possible to provide a method of manufacturing a liquid crystal display device which can reduce the amount of light irradiated in the alignment treatment of the photoalignment film and obtain good contrast and viewing angle characteristics.

本實施形態之液晶顯示裝置之製造方法之特徵在於：其係具備光配向膜之液晶顯示裝置之製造方法，且依序包括：步驟(1)，其於基板上形成含有2種以上之聚合物及溶劑之光配向膜材料之膜；步驟(2)，其對上述膜進行使上述溶劑蒸發之預焙燒；步驟(3)，其對預焙燒後之上述膜自低溫至高溫於複數個溫度下階段性地進行正式焙燒；及步驟(4)，其對正式焙燒後之上述膜進行偏光照射；並且上述2種以上之聚合物中之至少一者為側鏈具有光官能基之光反應性聚合物。 The method for producing a liquid crystal display device of the present embodiment is characterized in that it is a method for producing a liquid crystal display device including a photo-alignment film, and includes, in order, a step (1) of forming a polymer containing two or more kinds on a substrate. And a film of the light-aligning film material of the solvent; the step (2), the pre-baking of the film to evaporate the solvent; and the step (3), the film is pre-baked from a low temperature to a high temperature at a plurality of temperatures Formally performing the main calcination; and the step (4) of polarizing the film after the main calcination; and at least one of the two or more polymers is a photoreactive polymerization having a photofunctional group in the side chain Things.

關於上述步驟(1)，例如使用噴墨方式、或藉由旋轉塗佈法進行塗佈之方法、或藉由軟版方式進行印刷(轉印)之方法等。而且，藉由該等方法，以藉由之後之步驟可作為光配向膜發揮作用之方式，使用上述光配向膜材料於基板上形成上述膜即可。上述膜之形成條件只要根據上述膜之形成方法等適當設定即可。又，上述膜之膜厚等亦與通常設定之光配向膜之膜厚等相同即可。又，關於形成有上述膜之基板，亦為實施用以形成光配向膜之處理之基板即可，可為經進行各種處理之基板。 The above step (1) is, for example, an inkjet method, a method of coating by a spin coating method, a method of performing printing (transfer) by a soft plate method, or the like. Further, by such a method, the film may be formed on the substrate by using the photo-alignment film material in such a manner that the subsequent step can function as a photo-alignment film. The conditions for forming the film may be appropriately set according to the method for forming the film or the like. Further, the film thickness of the film or the like may be the same as the film thickness of the photoalignment film which is normally set. Further, the substrate on which the film is formed may be a substrate on which a process for forming a photo-alignment film is performed, and may be a substrate subjected to various treatments.

上述步驟(1)中使用之上述光配向膜材料係含有2種以上之聚合物及溶劑者，且為於經過上述步驟(1)~(4)後構成光配向膜者。即，上述光配向膜係藉由照射光而上述聚合物中之光官能基產生化學反應，表現出對液晶分子之配向限制力之膜。 The photo-alignment film material used in the above step (1) contains two or more kinds of polymers and solvents, and is a photo-alignment film after the above steps (1) to (4). In other words, the photo-alignment film is a film which chemically reacts with a photofunctional group in the polymer by irradiation with light, and exhibits an alignment regulating force against liquid crystal molecules.

上述2種以上之聚合物中之至少一者為側鏈具有光官能基之光反應性聚合物。藉由側鏈具有光官能基，即便於正式焙燒步驟後進行偏光照射步驟，亦可使聚合物側鏈進行再排列，對配向膜賦予單軸各向異性。光反應性聚合物較佳為於適當地進行正式焙燒時，具有配向膜所要求之充分之特性。再者，於光反應性聚合物於主鏈具有光官能基之情形時，藉由正式焙燒步驟而配向膜成為高密度之聚合物膜，故而即便之後進行偏光照射，亦難以使聚合物主鏈進行再排列而對配向膜賦予單軸各向異性，於配向處理中必需非常多之偏光照射。 At least one of the above two or more polymers is a photoreactive polymer having a photofunctional group in a side chain. By having a photofunctional group in the side chain, even if the polarizing irradiation step is performed after the main baking step, the polymer side chains can be rearranged to impart uniaxial anisotropy to the alignment film. The photoreactive polymer preferably has sufficient characteristics required for the alignment film when it is appropriately subjected to the main firing. Further, when the photoreactive polymer has a photofunctional group in the main chain, the film is aligned into a high-density polymer film by a main calcination step, so that it is difficult to make the polymer main chain even after polarized light irradiation. The alignment is performed to impart uniaxial anisotropy to the alignment film, and a large amount of polarized light irradiation is required in the alignment treatment.

作為上述光官能基，可為選自由肉桂酸酯基、查耳酮基、香豆素基、茋基、酚酯基及偶氮苯基所組成之群中之至少1個官能基。其中，較佳為肉桂酸酯基。 The photofunctional group may be at least one functional group selected from the group consisting of a cinnamate group, a chalcone group, a coumarin group, a thiol group, a phenol ester group, and an azophenyl group. Among them, a cinnamate group is preferred.

上述光反應性聚合物可具有選自由聚矽氧烷、聚醯胺酸、聚醯亞胺及順丁烯二醯亞胺所組成之群中之至少1種結構。 The photoreactive polymer may have at least one structure selected from the group consisting of polyoxyalkylene, polyglycolic acid, polyimine, and maleimide.

作為上述光反應性聚合物，例如可列舉具有下述化學式(1)所表示之結構之化合物。 The photoreactive polymer is, for example, a compound having a structure represented by the following chemical formula (1).

(式中，R1表示單鍵或二價有機基。 (wherein R1 represents a single bond or a divalent organic group.

R2表示一價有機基。 R2 represents a monovalent organic group.

R3表示-H、-F或一價有機基。 R3 represents -H, -F or a monovalent organic group.

n為2以上之整數)。 n is an integer of 2 or more).

上述二價有機基較佳為包含例如選自由伸烷基、醚基及酯基所組成之群中之至少一種。上述一價有機基較佳為包含例如選自由烷基、苯基、羰基、環氧基、醚基及酯基所組成之群中之至少一種。 The above divalent organic group preferably contains, for example, at least one selected from the group consisting of an alkylene group, an ether group, and an ester group. The monovalent organic group preferably contains, for example, at least one selected from the group consisting of an alkyl group, a phenyl group, a carbonyl group, an epoxy group, an ether group, and an ester group.

上述光反應性聚合物之比率相對於上述光配向膜材料所含有之固形物成分整體，可為5~30重量%。即便上述光反應性聚合物之比率為上述範圍，藉由經過上述步驟(1)~(4)，亦可於配向膜之液晶層側充分地使光反應性聚合物露出。又，藉由減少光反應性聚合物之調配量，可使對電氣特性改善有效果之非光反應性聚合物之比率較高，故而可使VHR(voltage holding ratio，電壓保持率)更良好。又，於上述光反應性聚合物例如為如吸收可見光波長區域之光之經著色之聚合物的情形時，藉由使相對於固形物成分整體之比率較小，可提高光配向膜之光透過率，可提昇液晶顯示面板之光透過率。 The ratio of the photoreactive polymer may be 5 to 30% by weight based on the total solid content of the photo-alignment film material. Even if the ratio of the photoreactive polymer is in the above range, the photoreactive polymer can be sufficiently exposed on the liquid crystal layer side of the alignment film by the above steps (1) to (4). Further, by reducing the amount of the photoreactive polymer, the ratio of the non-photoreactive polymer which is effective for improving the electrical characteristics can be made high, so that the VHR (voltage holding ratio) can be further improved. Further, in the case where the photoreactive polymer is, for example, a colored polymer which absorbs light in a wavelength region of visible light, light transmittance of the photoalignment film can be improved by making the ratio with respect to the entire solid content component small. The rate can increase the light transmittance of the liquid crystal display panel.

上述2種以上之聚合物可包含以聚醯胺酸及/或聚醯亞胺作為主鏈之非光反應性聚合物。上述非光反應性聚合物之比率相對於上述光配向膜材料所含有之固形物成分整體，可為70~95重量%。上述非光反應性聚合物由於對電氣特性改善有效果，故而藉由將上述非光反應性聚合物之比率設為上述範圍，可使VHR更良好。 The above two or more kinds of polymers may include a non-photoreactive polymer having polyamine and/or polyimine as a main chain. The ratio of the non-photoreactive polymer may be 70 to 95% by weight based on the total solid content of the photo-alignment film material. Since the non-photoreactive polymer is effective in improving electrical characteristics, the VHR can be further improved by setting the ratio of the non-photoreactive polymer to the above range.

尤其是相對於上述光配向膜材料所含有之固形物成分整體，將上述光反應性聚合物之比率設為5~30重量%，且將非光反應性聚合物之比率設為70~95重量%，藉此可同時實現良好之對比度及良好之VHR。 In particular, the ratio of the photoreactive polymer to the total amount of the solid content component contained in the photo-alignment film material is 5 to 30% by weight, and the ratio of the non-photoreactive polymer is 70 to 95% by weight. %, which achieves good contrast and good VHR at the same time.

上述溶劑只要為可使上述2種以上之聚合物溶解或分散之液體(室溫時)則並無特別限定，藉由上述步驟(2)及(3)自光配向膜材料中去除。再者，上述溶劑不僅可包含適於使上述聚合物溶解之成分(良溶劑)，亦可包含適於將上述光配向膜材料於基板上以均一之厚度進行擴散之成分(不良溶劑)等，較佳為該等 之混合物。上述溶劑可為選自由N-甲基-2-吡咯啶酮、N-乙基-吡咯啶酮及γ-丁內酯所組成之群中之至少1種化合物與選自由丁基溶纖素、二乙二醇二***、二異丁基酮及其結構異構物、乙二醇單丁醚、丙二醇單丁醚以及二丙酮醇所組成之群中之至少1種化合物的混合物。 The solvent is not particularly limited as long as it is a liquid which can dissolve or disperse the above two or more kinds of polymers (at room temperature), and is removed from the photo-alignment film material by the above steps (2) and (3). Further, the solvent may include not only a component (good solvent) suitable for dissolving the polymer, but also a component (poor solvent) suitable for diffusing the light alignment film material on a substrate to a uniform thickness. Preferably such a mixture. The solvent may be at least one compound selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-pyrrolidone and γ-butyrolactone and is selected from the group consisting of butyl cellosolve, diethyl A mixture of at least one compound selected from the group consisting of glycol diethyl ether, diisobutyl ketone and structural isomers thereof, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, and diacetone alcohol.

可於上述光配向膜材料中預先添加環氧樹脂、羧酸、胺、丙烯酸酯或甲基丙烯酸酯等具有複數個官能基之單體。藉此，可提昇長期可靠性。該單體係對上述聚合物作為交聯劑發揮作用，於光配向膜中形成網狀結構。藉此，可抑制光配向膜中或基板(例如彩色濾光片基板)等中所包含之雜質溶出液晶中，於長時間使用液晶顯示裝置之過程中，充分地抑制電壓保持率之降低。 A monomer having a plurality of functional groups such as an epoxy resin, a carboxylic acid, an amine, an acrylate or a methacrylate may be added to the above-mentioned photo-alignment film material. This will improve long-term reliability. The single system acts as a crosslinking agent for the above polymer to form a network structure in the photoalignment film. Thereby, it is possible to suppress the elution of the impurities in the optical alignment film or the impurities contained in the substrate (for example, the color filter substrate), and to sufficiently suppress the decrease in the voltage holding ratio during the use of the liquid crystal display device for a long period of time.

上述基板包含具備薄膜電晶體元件之薄膜電晶體陣列基板，上述薄膜電晶體元件可具有包含氧化物半導體之半導體層。 The substrate includes a thin film transistor array substrate including a thin film transistor element, and the thin film transistor element may have a semiconductor layer including an oxide semiconductor.

氧化物半導體具有遷移率高於非晶矽，特性偏差亦較小之特徵。因此，包含氧化物半導體之薄膜電晶體元件較包含非晶矽之薄膜電晶體元件可以更高速進行驅動，驅動頻率較高，可減小占1像素之比率，故而適於更高精細之下一代顯示裝置之驅動。又，氧化物半導體膜具有由於較多晶矽膜藉由簡便之製程形成，故而亦可應用於必需大面積之裝置之優點。因此，於上述基板包含具備薄膜電晶體元件之薄膜電晶體陣列基板，且薄膜電晶體元件具有包含氧化物半導體之半導體層之情形時，可製造可發揮本發明之一態樣之效果，並且實現高速驅動化之液晶顯示裝置。 The oxide semiconductor has a characteristic that the mobility is higher than that of the amorphous germanium, and the characteristic deviation is also small. Therefore, a thin film transistor device including an oxide semiconductor can be driven at a higher speed than a thin film transistor device including an amorphous germanium, and has a higher driving frequency and can reduce a ratio of 1 pixel, so that it is suitable for a higher-definition next generation. The drive of the display device. Further, since the oxide semiconductor film is formed by a simple process by a plurality of wafers, it can be applied to a device having a large area. Therefore, when the substrate includes a thin film transistor array substrate including a thin film transistor element and the thin film transistor element has a semiconductor layer including an oxide semiconductor, an effect of one aspect of the present invention can be produced and realized. High-speed drive liquid crystal display device.

又，作為氧化物半導體之組成，例如可為包含銦(In)、鎵(Ga)、鋅(Zn)及氧(O)之化合物(In-Ga-Zn-O)、包含銦(In)、錫(Tin)、鋅(Zn)及氧(O)之化合物(In-Tin-Zn-O)、或包含銦(In)、鋁(Al)、鋅(Zn)及氧(O)之化合物(In-Al-Zn-O)等。 Further, the composition of the oxide semiconductor may be, for example, a compound containing indium (In), gallium (Ga), zinc (Zn), and oxygen (O) (In-Ga-Zn-O), or indium (In). Tin (Tin), zinc (Zn) and oxygen (O) compounds (In-Tin-Zn-O), or compounds containing indium (In), aluminum (Al), zinc (Zn) and oxygen (O) ( In-Al-Zn-O) and the like.

又，於氧化物半導體包含水分之情形時，有產生其氧比率降低，特性發生變化之問題之情況。因此，於水分滲入至液晶顯示面板內之情形時，較佳為亦以氧化物半導體不包含水分之方式從而上述光配向膜材料具有耐水性。作為具有耐水性之聚合物，適宜地使用具有聚醯亞胺骨架之聚合物。 Further, when the oxide semiconductor contains moisture, there is a problem that the oxygen ratio is lowered and the characteristics are changed. Therefore, when moisture penetrates into the liquid crystal display panel, it is preferable that the photo-alignment film material has water resistance so that the oxide semiconductor does not contain moisture. As the polymer having water resistance, a polymer having a polyimine skeleton is suitably used.

上述步驟(2)(以下，亦稱為預焙燒步驟)例如為對上述膜進行加熱及乾燥，使上述溶劑蒸發者。此處，可藉由預焙燒步驟部分地去除上述溶劑，亦可實質上完全去除。又，預焙燒步驟例如藉由設定為特定之溫度之加熱板或烘烤爐等加熱裝置進行。藉由進行上述預焙燒步驟，可使光配向膜之膜厚均一，可使顯示品質良好。 The above step (2) (hereinafter also referred to as a pre-baking step) is, for example, heating and drying the film to evaporate the solvent. Here, the solvent may be partially removed by a pre-baking step, or may be substantially completely removed. Further, the pre-baking step is performed, for example, by a heating device such as a hot plate or a baking oven set to a specific temperature. By performing the above-described pre-baking step, the film thickness of the photo-alignment film can be made uniform, and the display quality can be improved.

根據上述步驟(3)(以下，亦稱為正式焙燒步驟)，自低溫至高溫於複數個溫度下階段性地進行處理，藉此可充分地去除上述溶劑，促進光反應性聚合物與其他聚合物之層分離。因此，可於配向膜之液晶層側充分地使光反應性聚合物露出，於之後之偏光照射步驟中可高效率地使側鏈進行再排列。正式焙燒步驟例如藉由設定為特定之溫度之加熱板或烘烤爐等加熱裝置進行。 According to the above step (3) (hereinafter, also referred to as a main calcination step), the treatment is carried out stepwise from a low temperature to a high temperature at a plurality of temperatures, whereby the solvent can be sufficiently removed to promote the photoreactive polymer and other polymerization. The layer of matter separates. Therefore, the photoreactive polymer can be sufficiently exposed on the liquid crystal layer side of the alignment film, and the side chains can be efficiently rearranged in the subsequent polarized light irradiation step. The main baking step is performed, for example, by a heating device such as a heating plate or a baking oven set to a specific temperature.

上述「自低溫至高溫於複數個溫度下階段性地進行正式焙燒」係指例如以具有複數個不同之溫度之恆溫時間之方式階段性地進行，或按照以實質上於複數個溫度下進行加熱之方式改變升溫速度等之刻意操作之溫度分佈而進行正式焙燒。此正式焙燒並非是例如針對形成有上述膜之基板，使用設定為特定之溫度之加熱板或烘烤爐等加熱裝置，按照於如可謂僅進行加熱之情況下產生之溫度分佈、或於單一溫度下進行加熱等之溫度分佈而並非按照如上所述之刻意操作之溫度分佈而進行正式焙燒。此處，恆溫時間例如可意指於±5℃之溫度範圍內保持1分鐘以上之加熱狀態之時間。 The above-mentioned "stage-to-stage calcination from a low temperature to a high temperature at a plurality of temperatures" means, for example, stepwise in a manner of a constant temperature having a plurality of different temperatures, or heating at substantially a plurality of temperatures. The main baking is performed by changing the temperature distribution of the deliberate operation such as the temperature increase rate. The main firing is not, for example, a heating device such as a heating plate or a baking oven set to a specific temperature for the substrate on which the film is formed, and the temperature distribution generated when heating is performed only, or at a single temperature. The temperature distribution such as heating is performed, and the main baking is not performed in accordance with the temperature distribution intentionally operated as described above. Here, the constant temperature time may mean, for example, a time of maintaining a heating state of 1 minute or more in a temperature range of ±5 °C.

上述步驟(3)之正式焙燒步驟也可使用設定為不同之溫度之複數台加熱裝置進行。藉此，可適宜地對預焙燒後之上述膜自低溫至高溫於複數個溫度下階段性地進行正式焙燒。又，與使用1台加熱裝置之情形相比，可進一步提昇製造效率。 The main calcination step of the above step (3) can also be carried out using a plurality of heating devices set to different temperatures. Thereby, the film after prebaking can be suitably subjected to a preliminary baking stepwise from a low temperature to a high temperature at a plurality of temperatures. Moreover, the manufacturing efficiency can be further improved as compared with the case of using one heating device.

上述步驟(3)之正式焙燒步驟可使用1台加熱裝置一面依序變化為不同之溫度一面進行。藉此，可適宜地對預焙燒後之上述膜自低溫至高溫於複數個溫度下階段性地進行正式焙燒。又，與使用複數台加熱裝置之情形相比，可進一步縮小加熱裝置之設置面積，可提昇裝置佈局之自由度。 The main baking step of the above step (3) can be carried out by using one heating device while changing to a different temperature. Thereby, the film after prebaking can be suitably subjected to a preliminary baking stepwise from a low temperature to a high temperature at a plurality of temperatures. Moreover, compared with the case of using a plurality of heating devices, the installation area of the heating device can be further reduced, and the degree of freedom in device layout can be improved.

上述步驟(3)之正式焙燒步驟可使用具有存在溫度梯度之區域之加熱裝置，於上述加熱裝置內一面移動上述基板一面進行。藉此，可適宜地對預焙燒後之上述膜自低溫至高溫於複數個溫度下階段性地進行正式焙燒。 The main baking step of the above step (3) can be carried out by using a heating device having a region having a temperature gradient in which the substrate is moved while being inside the heating device. Thereby, the film after prebaking can be suitably subjected to a preliminary baking stepwise from a low temperature to a high temperature at a plurality of temperatures.

上述步驟(4)(以下，亦稱為偏光照射步驟)係對正式焙燒後之上述膜進行光配向處理者，可適宜地使用偏光紫外線，波長較佳為200nm~400nm，更佳為波長300nm~400nm。偏光照射量例如較佳為200mJ/cm2以下，更佳為100mJ/cm2以下，進而較佳為50mJ/cm2以下。 In the above step (4) (hereinafter, also referred to as a polarized light irradiation step), the photo-alignment treatment of the film after the main baking is performed, and a polarized ultraviolet ray may be suitably used, and the wavelength is preferably 200 nm to 400 nm, more preferably 300 nm. 400nm. The amount of polarized light irradiation is, for example, preferably 200 mJ/cm 2 or less, more preferably 100 mJ/cm 2 or less, still more preferably 50 mJ/cm 2 or less.

於本實施形態中，藉由預焙燒步驟及正式焙燒步驟，配向膜中之2種以上之聚合物之層分離較為充分，故而即便減小偏光照射量，亦可獲得對比度良好之液晶顯示裝置。又，由於在正式焙燒步驟後進行偏光照射步驟，故而不會引起配向膜之自組裝，可將配向膜之各向異性抑制為較低，結果為可獲得視角特性良好之液晶顯示裝置。 In the present embodiment, the layer separation of the two or more types of polymers in the alignment film is sufficient by the pre-baking step and the main baking step. Therefore, even if the amount of polarized light is reduced, a liquid crystal display device having good contrast can be obtained. Further, since the polarizing irradiation step is performed after the main baking step, the alignment film is not self-assembled, and the anisotropy of the alignment film can be suppressed to be low, and as a result, a liquid crystal display device having excellent viewing angle characteristics can be obtained.

上述液晶顯示裝置可為預傾角實質上為0°之橫向電場效應(IPS)模式或邊緣場切換(FFS)模式。構成此種液晶顯示裝置之上述光配向膜可為於相對於基板之主表面水平之方向使液晶分子配向者(以下，亦稱為水平光配向膜)。水平光 配向膜只要為使至少接近之液晶分子相對於水平光配向膜之膜面實質上水平地配向者即可。預傾角實質上為0°係指例如液晶分子之預傾角相對於水平光配向膜之膜面為1°以下。 The above liquid crystal display device may be a transverse electric field effect (IPS) mode or a fringe field switching (FFS) mode in which the pretilt angle is substantially 0°. The light alignment film constituting the liquid crystal display device may be a liquid crystal molecule alignment direction (hereinafter also referred to as a horizontal light alignment film) in a horizontal direction with respect to a main surface of the substrate. Horizontal light The alignment film may be such that at least liquid crystal molecules are aligned substantially horizontally with respect to the film surface of the horizontal light alignment film. The fact that the pretilt angle is substantially 0° means that, for example, the pretilt angle of the liquid crystal molecules is 1° or less with respect to the film surface of the horizontal light alignment film.

上述液晶分子可為具有正介電常數各向異性者，亦可為具有負介電常數各向異性者。正介電常數各向異性例如為△ε=1~20，負介電常數各向異性例如為△ε=-20~-1。 The liquid crystal molecules may have positive dielectric anisotropy or negative dielectric anisotropy. The positive dielectric anisotropy is, for example, Δε = 1 to 20, and the negative dielectric anisotropy is, for example, Δε = -20 to -1.

以下，揭示實施例，對本發明更詳細地進行說明，但本發明並不僅限定於該等實施例。又，以下之實施例可於不脫離本發明之主旨之範圍內適當組合，亦可進行變更。 Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples. Further, the following embodiments can be appropriately combined and changed without departing from the spirit and scope of the invention.

以下，依序對實施例1之液晶顯示裝置之製造方法進行說明。 Hereinafter, a method of manufacturing the liquid crystal display device of the first embodiment will be described in order.

(光配向膜形成用之基板) (substrate for forming a light alignment film)

準備具備FFS模式用之電極結構、In-Ga-Zn-O系氧化物半導體等之薄膜電晶體(TFT)基板、及配置有高度3.2μm之感光性間隔件之彩色濾光片(CF)基板。 A thin film transistor (TFT) substrate including an electrode structure for an FFS mode, an In-Ga-Zn-O-based oxide semiconductor, and a color filter (CF) substrate having a photosensitive spacer having a height of 3.2 μm is prepared. .

(光配向膜材料) (light alignment film material)

光配向膜材料準備含有光反應性聚合物、非光反應性聚合物及溶劑者。 The photo-alignment film material is prepared from a photoreactive polymer, a non-photoreactive polymer, and a solvent.

作為光反應性聚合物，使用主鏈具有聚矽氧烷且側鏈具有作為光官能基之肉桂酸酯基者。作為非光反應性聚合物，使用使1,2,3,4-環丁烷四羧酸二酐(CBDA)及包含聯苯結構之二胺進行反應而獲得之聚醯胺酸。作為溶劑，使用將N-甲基-2-吡咯啶酮與乙二醇單丁醚以重量比50：50進行混合而成者。光配向膜材料中之固形物成分濃度設為4重量%。光反應性聚合物與非光反應性聚合物 之調配比設為3：7。即，相對於光配向膜材料所含有之固形物成分整體，光反應性聚合物之比率為30重量%，非光反應性聚合物之比率為70重量%。 As the photoreactive polymer, those having a polyoxyalkylene main chain and having a cinnamate group as a photofunctional group in the side chain are used. As the non-photoreactive polymer, polylysine obtained by reacting 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) and a diamine containing a biphenyl structure is used. As the solvent, N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether were mixed at a weight ratio of 50:50. The solid content concentration in the photo-alignment film material was set to 4% by weight. Photoreactive polymer and non-photoreactive polymer The ratio is set to 3:7. That is, the ratio of the photoreactive polymer to the entire solid content component contained in the photo-alignment film material was 30% by weight, and the ratio of the non-photoreactive polymer was 70% by weight.

(形成光配向膜材料之膜之步驟) (Step of forming a film of photo-alignment film material)

於TFT基板及CF基板上藉由旋轉塗佈法形成光配向膜材料之膜。 A film of a photo-alignment film material is formed on the TFT substrate and the CF substrate by a spin coating method.

(預焙燒步驟) (pre-baking step)

繼而，對光配向膜材料之膜於70℃下進行預焙燒2分鐘。預焙燒係使用AS ONE公司製造之加熱板(商品名：EC-1200N)而進行。又，預焙燒步驟後之膜之膜厚為100nm左右。 Then, the film of the photo-alignment film material was pre-baked at 70 ° C for 2 minutes. The prebaking was carried out using a heating plate (trade name: EC-1200N) manufactured by AS ONE. Further, the film thickness of the film after the pre-baking step is about 100 nm.

(正式焙燒步驟) (formal roasting step)

對預焙燒步驟後之膜以兩個階段進行正式焙燒。正式焙燒步驟之第一階段係於110℃下進行15分鐘，第二階段係於200℃下進行30分鐘。正式焙燒係使用AS ONE公司製造之加熱板(商品名：EC-1200N)而進行。 The film after the pre-baking step is subjected to a main calcination in two stages. The first stage of the formal calcination step was carried out at 110 ° C for 15 minutes and the second stage was carried out at 200 ° C for 30 minutes. The main baking was carried out using a heating plate (trade name: EC-1200N) manufactured by AS ONE.

(偏光照射步驟) (polarized illumination step)

對正式焙燒步驟後之膜自法線方向照射直線偏光紫外線。直線偏光紫外線之照射量係於中心波長313nm附近設為30mJ/cm2。再者，於TFT基板中，以偏光照射方向與FFS模式用之電極之狹縫方向大致垂直之方式照射直線偏光紫外線。 The film after the main baking step is irradiated with linear polarized ultraviolet rays from the normal direction. The amount of irradiation of the linearly polarized ultraviolet rays was set to 30 mJ/cm 2 in the vicinity of the center wavelength of 313 nm. Further, in the TFT substrate, linearly polarized ultraviolet rays are irradiated so that the direction in which the polarized light is irradiated is substantially perpendicular to the slit direction of the electrode for the FFS mode.

於偏光照射步驟後，於TFT基板上藉由點膠機對熱硬化密封材料進行繪圖，與CF基板貼合後，封入包含具有正介電常數各向異性之液晶分子之液晶材料。所使用之液晶材料之介電常數各向異性為7。TFT基板與CF基板係以照射之偏光紫外線之偏光方向相互平行之方式進行貼合。之後，藉由於130℃下加熱40分鐘，進行熱硬化密封材料之硬化及液晶分子之再配向處理，獲得液晶分子均一地單軸配向之液晶顯示面板。 After the polarizing irradiation step, the thermosetting sealing material is drawn on the TFT substrate by a dispenser, and after bonding with the CF substrate, a liquid crystal material containing liquid crystal molecules having positive dielectric anisotropy is sealed. The dielectric constant of the liquid crystal material used was 7. The TFT substrate and the CF substrate are bonded so that the polarization directions of the polarized ultraviolet rays to be irradiated are parallel to each other. Thereafter, by heating at 130 ° C for 40 minutes, the thermosetting sealing material is cured and the liquid crystal molecules are realigned to obtain a liquid crystal display panel in which the liquid crystal molecules are uniformly uniaxially aligned.

之後，藉由於液晶顯示面板適當配置偏光板、背光源等構件，完成實施例1之液晶顯示裝置。 Thereafter, the liquid crystal display device of the first embodiment is completed by appropriately arranging members such as a polarizing plate and a backlight in the liquid crystal display panel.

關於實施例2之液晶顯示裝置之製造方法，光反應性聚合物之結構不同，除該方面以外，與實施例1之液晶顯示裝置之製造方法相同。於實施例2中，作為光反應性聚合物，使用主鏈具有聚醯胺酸且側鏈具有作為光官能基之肉桂酸酯基者。光反應性聚合物與非光反應性聚合物之調配比設為3：7。即，相對於光配向膜材料所含有之固形物成分整體，光反應性聚合物之比率為30重量%，非光反應性聚合物之比率為70重量%。 The method for producing a liquid crystal display device of Example 2 is the same as the method for producing a liquid crystal display device of Example 1, except that the structure of the photoreactive polymer is different. In Example 2, as the photoreactive polymer, those having a polyamine acid in the main chain and a cinnamate group as a photofunctional group in the side chain were used. The compounding ratio of the photoreactive polymer to the non-photoreactive polymer was set to 3:7. That is, the ratio of the photoreactive polymer to the entire solid content component contained in the photo-alignment film material was 30% by weight, and the ratio of the non-photoreactive polymer was 70% by weight.

關於比較例1之液晶顯示裝置之製造方法，光反應性聚合物之結構不同，除該方面以外，與實施例1之液晶顯示裝置之製造方法相同。於比較例1中，作為光反應性聚合物，使用主鏈具有聚醯胺酸且主鏈具有作為光官能基之肉桂酸酯基者。光反應性聚合物與非光反應性聚合物之調配比設為3：7。即，相對於光配向膜材料所含有之固形物成分整體，光反應性聚合物之比率為30重量%，非光反應性聚合物之比率為70重量%。 The method for producing a liquid crystal display device of Comparative Example 1 is the same as the method for producing a liquid crystal display device of Example 1, except that the structure of the photoreactive polymer is different. In Comparative Example 1, as the photoreactive polymer, those having a polyamine acid in the main chain and a cinnamate group as a photofunctional group in the main chain were used. The compounding ratio of the photoreactive polymer to the non-photoreactive polymer was set to 3:7. That is, the ratio of the photoreactive polymer to the entire solid content component contained in the photo-alignment film material was 30% by weight, and the ratio of the non-photoreactive polymer was 70% by weight.

對藉由實施例1、2及比較例1之液晶顯示裝置之製造方法所製造之液晶顯示裝置評價對比度。 The contrast was evaluated on the liquid crystal display devices manufactured by the methods of manufacturing the liquid crystal display devices of Examples 1 and 2 and Comparative Example 1.

(對比度) (contrast)

對比度(CR)係以(對比度)=(白顯示時之亮度)/(黑顯示時之亮度)定義。白顯示時設為成為最大亮度之施加電壓狀態，黑顯示時設為不施加電壓狀態。於亮度之測定中使用Topcon公司製造之分光放射儀(商品名：SR-UL2)。若對比度之值為1000以上，則判斷為作為製品不存在問題。將對比度之值為1000以上設為○，將未達1000設為×。 Contrast (CR) is defined by (contrast) = (brightness in white display) / (brightness in black display). In the case of white display, the applied voltage state is set to the maximum brightness, and in the case of black display, the voltage is not applied. A spectroradiometer (trade name: SR-UL2) manufactured by Topcon Corporation was used for the measurement of the brightness. If the value of the contrast is 1000 or more, it is judged that there is no problem as a product. The contrast value is set to 1000 or more to ○, and the less than 1000 is set to ×.

將實施例1、2及比較例1中之對比度之評價結果示於下述表1。 The evaluation results of the contrasts in Examples 1 and 2 and Comparative Example 1 are shown in Table 1 below.

如表1所示，實施例1及2中之對比度為1200，即便偏光照射量較低，亦可獲得作為製品而合適之對比度。比較例1中之對比度為100以下，液晶分子幾乎未進行配向。若使用如比較例1般主鏈具有光官能基之光反應性聚合物，則於正式焙燒步驟後之偏光照射步驟中即便照射直線偏光紫外線，亦難以使液晶分子之配向單向地排列。因此，光配向膜之感度明顯變差，無法獲得良好之對比度。 As shown in Table 1, the contrast ratios in Examples 1 and 2 were 1200, and even if the amount of polarized light irradiation was low, a suitable contrast as a product was obtained. In Comparative Example 1, the contrast was 100 or less, and liquid crystal molecules were hardly aligned. When the photoreactive polymer having a photofunctional group in the main chain as in Comparative Example 1 is used, it is difficult to align the alignment of the liquid crystal molecules in a unidirectional manner even when the linearly polarized ultraviolet ray is irradiated in the polarized light irradiation step after the main baking step. Therefore, the sensitivity of the photo-alignment film is remarkably deteriorated, and a good contrast cannot be obtained.

關於比較例2之液晶顯示裝置之製造方法，光反應性聚合物之結構不同，正式焙燒步驟與偏光照射步驟之順序不同，僅於單一溫度下進行1個階段之正式焙燒步驟，除該等方面以外，與實施例1之液晶顯示裝置之製造方法相同。 In the method for producing a liquid crystal display device of Comparative Example 2, the structure of the photoreactive polymer is different, and the order of the main baking step and the polarizing step is different, and only one stage of the main baking step is performed at a single temperature, except for these aspects. Other than the method of manufacturing the liquid crystal display device of the first embodiment.

於比較例2中，作為光反應性聚合物，使用主鏈具有甲基丙烯酸酯進行聚合而成之結構且側鏈具有作為光官能基之肉桂酸酯基者。與實施例1同樣地於TFT基板及CF基板上形成光配向膜材料之膜，進行預焙燒步驟。 In Comparative Example 2, as the photoreactive polymer, a structure in which a main chain has a methacrylate and a structure in which a side chain has a cinnamate group as a photofunctional group is used. A film of a photo-alignment film material was formed on the TFT substrate and the CF substrate in the same manner as in Example 1, and a pre-baking step was performed.

(偏光照射步驟) (polarized illumination step)

對TFT基板及CF基板上之預焙燒步驟後之膜自法線方向照射直線偏光紫外線。直線偏光紫外線之照射量係於中心波長313nm附近設為5mJ/cm2。 The film after the pre-baking step on the TFT substrate and the CF substrate is irradiated with linearly polarized ultraviolet rays from the normal direction. The amount of irradiation of the linearly polarized ultraviolet rays was set to 5 mJ/cm 2 in the vicinity of the center wavelength of 313 nm.

(正式焙燒步驟) (formal roasting step)

對TFT基板及CF基板上之偏光照射步驟後之膜進行正式焙燒。正式焙燒步驟係於140℃下進行20分鐘。 The film after the polarizing irradiation step on the TFT substrate and the CF substrate is subjected to main baking. The formal calcination step was carried out at 140 ° C for 20 minutes.

對藉由實施例1及比較例2之液晶顯示裝置之製造方法所製造之液晶顯示裝置評價對比度、視角特性及延遲。對比度之測定係藉由上述方法進行。 The liquid crystal display device manufactured by the method for manufacturing a liquid crystal display device of Example 1 and Comparative Example 2 was evaluated for contrast, viewing angle characteristics, and retardation. The measurement of contrast is carried out by the above method.

(視角特性) (viewing characteristics)

視角特性係藉由算出相對於液晶顯示裝置之正面亮度之斜向亮度比，評價發白之程度而進行。使用ELDIM公司製造之視角測定裝置(商品名：EZ-contrast)，於極角60°、方位角30°下測定64灰階顯示時之面板之正面亮度T正面及斜向亮度T斜向，計算T斜向/T正面。例如，於亮度比為2之情形時，意味著相對於正面，斜向之亮度成為2倍。若亮度比為2以上，則判斷為作為製品存在問題。將T斜向/T正面大於2設為○，將2以下設為×。 The viewing angle characteristics were evaluated by calculating the oblique luminance ratio with respect to the front luminance of the liquid crystal display device and evaluating the degree of blushing. Using the viewing angle measuring device (trade name: EZ-contrast) manufactured by ELDIM Co., Ltd., the front side luminance T front and the oblique brightness T oblique direction of the panel when the gray scale display is displayed at a polar angle of 60° and an azimuth angle of 30° are calculated. T oblique / T front . For example, when the luminance ratio is 2, it means that the luminance in the oblique direction is twice as large as the front surface. When the luminance ratio is 2 or more, it is determined that there is a problem as a product. The T oblique direction /T front surface is greater than 2 and is set to ○, and 2 or less is set to ×.

(延遲) (delay)

延遲(相位差)之評價係對形成有光配向膜之TFT基板及CF基板進行延遲測定，評價光配向膜之延遲及軸方位。使用Axometrics公司製造之偏光、相位差分析/評價系統(AxoScan)，自基板之法線方向以波長550nm進行測定。若延遲為10nm以下，則顯示品質良好。關於延遲之遲相軸之方向，實施例1、比較例2均為與配向照射偏光方向正交之面內方向。 The evaluation of the retardation (phase difference) was performed by delay measurement of the TFT substrate and the CF substrate on which the photoalignment film was formed, and the retardation and the axial orientation of the photoalignment film were evaluated. The polarization and phase difference analysis/evaluation system (AxoScan) manufactured by Axometrics Co., Ltd. was used to measure at a wavelength of 550 nm from the normal direction of the substrate. When the retardation is 10 nm or less, the display quality is good. Regarding the direction of the retardation phase axis, the first embodiment and the second comparative example are in the in-plane direction orthogonal to the alignment irradiation polarization direction.

將實施例1及比較例2中之對比度、視角特性及延遲之評價結果示於下述表2。 The evaluation results of contrast, viewing angle characteristics, and retardation in Example 1 and Comparative Example 2 are shown in Table 2 below.

[表2] [Table 2]

如表2所示，實施例1及比較例2中之對比度為1200，較為良好。另一方面，關於實施例1中之視角特性，T斜向/T正面較為良好為1.3，相對於此，關於比較例2中之視角特性，T斜向/T正面為2.1，確認到明顯之發白。又，實施例1中之延遲非常小為0.1nm，另一方面，比較例2中之延遲非常大為20nm。於比較例2中，於偏光照射步驟後進行正式焙燒步驟，使構成光配向膜之聚合物進行自組裝。其結果為放大配向膜之各向異性，延遲變得非常大，視角特性變差。於實施例1之液晶顯示裝置之製造方法中，成功獲得可將光配向膜之延遲抑制為較低且視角特性良好之液晶顯示裝置。 As shown in Table 2, the contrast ratios in Example 1 and Comparative Example 2 were 1200, which was good. On the other hand, regarding the viewing angle characteristic in the first embodiment, the T oblique direction /T front surface is relatively good at 1.3. On the other hand, regarding the viewing angle characteristic in the comparative example 2, the T oblique direction /T front side is 2.1, and it is confirmed that it is obvious. White. Further, the retardation in Example 1 was very small at 0.1 nm, and on the other hand, the retardation in Comparative Example 2 was very large at 20 nm. In Comparative Example 2, a main baking step was performed after the polarized light irradiation step, and the polymer constituting the photoalignment film was self-assembled. As a result, the anisotropy of the alignment film is enlarged, the retardation becomes extremely large, and the viewing angle characteristics are deteriorated. In the method for producing a liquid crystal display device of the first embodiment, a liquid crystal display device which can suppress the retardation of the photoalignment film to be low and has excellent viewing angle characteristics is successfully obtained.

實施例3-1之液晶顯示裝置之製造方法係於90℃下進行正式焙燒步驟之第一階段15分鐘，除該方面以外，與實施例1之液晶顯示裝置之製造方法相同。 The manufacturing method of the liquid crystal display device of Example 3-1 was carried out at the first stage of the main baking step at 90 ° C for 15 minutes, and the manufacturing method of the liquid crystal display device of Example 1 was the same as the above.

實施例3-2之液晶顯示裝置之製造方法係於130℃下進行正式焙燒步驟之第一階段15分鐘，除該方面以外，與實施例1之液晶顯示裝置之製造方法相同。 The manufacturing method of the liquid crystal display device of Example 3-2 was carried out at 130 ° C for the first stage of the main baking step for 15 minutes, and the manufacturing method of the liquid crystal display device of Example 1 was the same as the above.

實施例3-3之液晶顯示裝置之製造方法係於150℃下進行正式焙燒步驟之第一階段15分鐘，除該方面以外，與實施例1之液晶顯示裝置之製造方法相同。 The manufacturing method of the liquid crystal display device of Example 3-3 was carried out at 150 ° C for 15 minutes in the first stage of the main baking step, except for the above, the manufacturing method of the liquid crystal display device of Example 1 was the same.

實施例3-4之液晶顯示裝置之製造方法係於170℃下進行正式焙燒步驟之第一階段15分鐘，除該方面以外，與實施例1之液晶顯示裝置之製造方法相同。 The manufacturing method of the liquid crystal display device of Example 3-4 was carried out at the first stage of the main baking step at 170 ° C for 15 minutes, and the manufacturing method of the liquid crystal display device of Example 1 was the same as the above.

比較例3之液晶顯示裝置之製造方法係僅於單一溫度下進行1個階段之正式焙燒步驟，除該方面以外，與實施例1之液晶顯示裝置之製造方法相同。 於比較例3中，對TFT基板及CF基板上之預焙燒步驟後之膜於200℃下進行正式焙燒30分鐘。 The manufacturing method of the liquid crystal display device of the comparative example 3 is the same as the manufacturing method of the liquid crystal display device of the first embodiment except that the one-stage main baking step is performed at a single temperature. In Comparative Example 3, the film after the pre-baking step on the TFT substrate and the CF substrate was subjected to main baking at 200 ° C for 30 minutes.

對藉由實施例1、實施例3-1~3-4及比較例3之液晶顯示裝置之製造方法所製造之液晶顯示裝置評價對比度。對比度之測定係藉由上述方法進行。將評價結果示於下述表3。 The liquid crystal display device manufactured by the method for producing a liquid crystal display device of Example 1, Examples 3-1 to 3-4, and Comparative Example 3 was evaluated for contrast. The measurement of contrast is carried out by the above method. The evaluation results are shown in Table 3 below.

如表3所示，於正式焙燒步驟僅為1個階段之比較例3中，所製造之液晶顯示裝置之對比度不充分。於以1個階段進行正式焙燒之情形時，光配向膜之層分離不充分，光反應性聚合物與非光反應性聚合物混合存在，故而認為無法獲得充分之對比度。又，根據實施例1、實施例3-1~3-4之結果可確認到藉由以90℃以上且170℃以下進行正式焙燒之第一階段，所製造之液晶顯示裝置之對比度良好。 As shown in Table 3, in Comparative Example 3 in which the main baking step was only one stage, the contrast of the manufactured liquid crystal display device was insufficient. When the main baking is performed in one stage, the layer separation of the photo-alignment film is insufficient, and the photo-reactive polymer and the non-photo-reactive polymer are mixed, and it is considered that sufficient contrast cannot be obtained. Further, according to the results of Example 1 and Examples 3-1 to 3-4, it was confirmed that the liquid crystal display device produced was excellent in contrast by the first stage of the main baking at 90 ° C or higher and 170 ° C or lower.

實施例4-1之液晶顯示裝置之製造方法係於220℃下進行正式焙燒步驟之第二階段30分鐘，除該方面以外，與實施例1之液晶顯示裝置之製造方法相同。 The manufacturing method of the liquid crystal display device of Example 4-1 is the same as the manufacturing method of the liquid crystal display device of Example 1 except that the second step of the main baking step was carried out at 220 ° C for 30 minutes.

實施例4-2之液晶顯示裝置之製造方法係於240℃下進行正式焙燒步驟之第二階段30分鐘，除該方面以外，與實施例1之液晶顯示裝置之製造方法相同。 The manufacturing method of the liquid crystal display device of Example 4-2 was carried out at 240 ° C for the second stage of the main baking step for 30 minutes, except for the above, the method of manufacturing the liquid crystal display device of Example 1 was the same.

對藉由實施例1、實施例4-1及4-2之液晶顯示裝置之製造方法所製造之液晶顯示裝置評價對比度及電壓保持率(VHR)。對比度之測定係藉由上述方法進行。 The contrast and voltage holding ratio (VHR) of the liquid crystal display device manufactured by the method for manufacturing a liquid crystal display device of Example 1, Examples 4-1 and 4-2 were evaluated. The measurement of contrast is carried out by the above method.

(電壓保持率) (voltage holding ratio)

電壓保持率係使用東陽技術公司製造之液晶物性評價系統(商品名：6254型)，於施加電壓5V、保持時間16.67ms、測定溫度60℃之條件下進行測定。 The voltage holding ratio was measured using a liquid crystal physical property evaluation system (trade name: 6254 type) manufactured by Toyo Denki Co., Ltd. under the conditions of an applied voltage of 5 V, a holding time of 16.67 ms, and a measurement temperature of 60 °C.

將實施例1、實施例4-1及4-2中之對比度及電壓保持率之評價結果示於下述表4。 The evaluation results of the contrast and voltage holding ratios in Example 1, Examples 4-1 and 4-2 are shown in Table 4 below.

如表4所示，藉由以200℃以上且240℃以下進行正式焙燒之第二階段，實施例1、實施例4-1及4-2中之對比度良好，VHR亦較高為99%以上之值。藉由 以200℃以上進行正式焙燒之第二階段，可充分地推進構成光配向膜之聚醯胺酸之醯亞胺化，故而認為所製造之液晶顯示裝置之VHR良好。 As shown in Table 4, the contrast in Example 1, Examples 4-1 and 4-2 was good by the second stage of the main baking at 200 ° C or higher and 240 ° C or lower, and the VHR was also higher than 99%. The value. By In the second stage of the main calcination at 200 ° C or higher, the ruthenium imidization of the polyamine which constitutes the photo-alignment film can be sufficiently promoted, and therefore the VHR of the liquid crystal display device produced is considered to be good.

實施例5-1之液晶顯示裝置之製造方法係於80℃下進行預焙燒步驟2分鐘，除該方面以外，與實施例1之液晶顯示裝置之製造方法相同。 The manufacturing method of the liquid crystal display device of Example 5-1 was carried out at 80 ° C for 2 minutes in the pre-baking step, and the manufacturing method of the liquid crystal display device of Example 1 was the same as the above.

實施例5-2之液晶顯示裝置之製造方法係於60℃下進行預焙燒步驟2分鐘，除該方面以外，與實施例1之液晶顯示裝置之製造方法相同。 The manufacturing method of the liquid crystal display device of Example 5-2 was carried out at 60 ° C for 2 minutes in the pre-baking step, and the method of manufacturing the liquid crystal display device of Example 1 was the same as the above.

實施例5-3之液晶顯示裝置之製造方法係於50℃下進行預焙燒步驟2分鐘，除該方面以外，與實施例1之液晶顯示裝置之製造方法相同。 The manufacturing method of the liquid crystal display device of Example 5-3 was carried out at 50 ° C for 2 minutes in the pre-baking step, and the manufacturing method of the liquid crystal display device of Example 1 was the same as the above.

對藉由實施例1及實施例5-1~5-3之液晶顯示裝置之製造方法所製造之液晶顯示裝置評價對比度。對比度之測定係藉由上述方法進行。將評價結果示於下述表5。 The liquid crystal display device manufactured by the method for manufacturing a liquid crystal display device of Example 1 and Examples 5-1 to 5-3 was evaluated for contrast. The measurement of contrast is carried out by the above method. The evaluation results are shown in Table 5 below.

如表5所示，可確認到藉由以50℃以上且80℃以下進行預焙燒，所製造之液晶顯示裝置之對比度良好。 As shown in Table 5, it was confirmed that the pre-baking by 50 ° C or more and 80 ° C or less resulted in a good contrast of the liquid crystal display device produced.

實施例6之液晶顯示裝置之製造方法係於對正式焙燒後之膜進行偏光照射之步驟後，進行於光配向膜上形成配向維持層之步驟，除該方面以外，與實施例1之液晶顯示裝置之製造方法相同。 The manufacturing method of the liquid crystal display device of the sixth embodiment is a step of forming a alignment maintaining layer on the photo-alignment film after the step of polarizing the film after the main baking, and the liquid crystal display of the first embodiment is the same as the liquid crystal display of the first embodiment. The manufacturing method of the device is the same.

(配向維持層之形成) (Formation of the alignment maintenance layer)

與實施例1同樣地進行偏光照射步驟，將TFT基板與CF基板貼合後，封入添加有作為聚合性單體之聯苯-4,4'-二基雙(2-丙烯酸甲酯)之液晶材料。聯苯-4,4'-二基雙(2-丙烯酸甲酯)之添加量相對於液晶材料總量設為0.5重量%。之後，與實施例1同樣地獲得液晶顯示面板。 In the same manner as in the first embodiment, the polarizing irradiation step was carried out, and the TFT substrate and the CF substrate were bonded together, and then a liquid crystal to which biphenyl-4,4'-diylbis(2-methyl acrylate) as a polymerizable monomer was added was sealed. material. The amount of biphenyl-4,4'-diylbis(2-methyl acrylate) added was set to 0.5% by weight based on the total amount of the liquid crystal material. Thereafter, a liquid crystal display panel was obtained in the same manner as in Example 1.

針對所獲得之液晶顯示面板，於不施加電壓之狀態下使用以350nm附近作為中心波長之黑光燈，以成為2J/cm2之方式照射紫外線，使液晶層中之聚合性單體進行聚合。 In the liquid crystal display panel obtained, a black light having a center wavelength of around 350 nm was used without applying a voltage, and ultraviolet rays were irradiated at 2 J/cm 2 to polymerize the polymerizable monomer in the liquid crystal layer.

對藉由實施例6之液晶顯示裝置之製造方法所製造之液晶顯示裝置評價殘像特性。 The afterimage characteristics were evaluated on the liquid crystal display device manufactured by the method for producing a liquid crystal display device of Example 6.

(殘像特性) (afterimage characteristics)

殘像特性係藉由殘像率進行評價。首先，設置可對同一液晶面板內施加不同之電壓之區域X及Y，對區域X施加亮度成為最大之電壓24小時。於對區域Y不施加電壓之狀態下放置24小時。之後，對區域X及Y分別施加亮度成為最大值之1%之電壓，測定亮度。將區域X之亮度設為T(x)，將區域Y之亮度設為T(y)。殘像率係根據△T=(｜T(x)-T(y)｜/T(y))×100進行計算。於亮度之測定中使用Canon公司製造之數位相機(商品名：EOS Kiss Digital NEF-S18-55IIU)。 The afterimage characteristics were evaluated by the afterimage rate. First, a region X and Y which can apply different voltages to the same liquid crystal panel are provided, and the maximum luminance is applied to the region X for 24 hours. It was left in a state where no voltage was applied to the region Y for 24 hours. Thereafter, a voltage having a luminance of 1% of the maximum value was applied to each of the regions X and Y, and the luminance was measured. The brightness of the area X is set to T(x), and the brightness of the area Y is set to T(y). The afterimage rate is calculated based on ΔT = (|T(x) - T(y) | / T(y)) × 100. A digital camera manufactured by Canon Co., Ltd. (trade name: EOS Kiss Digital NEF-S18-55IIU) was used for the measurement of the brightness.

實施例6中之殘像率非常良好為4%。又，使用10%之ND(neutral density，中性密度)濾光器，藉由目測之觀察亦未觀察到殘像。 The afterimage rate in Example 6 was very good at 4%. Further, a residual image was not observed by visual observation using a 10% ND (neutral density) filter.

關於實施例7之液晶顯示裝置之製造方法，液晶顯示裝置具備包含具有負介電常數各向異性之液晶分子之液晶層，且偏光照射步驟中之照射方向不同，除該等方面以外，與實施例1之液晶顯示裝置之製造方法相同。所使用之液晶材料之介電常數各向異性為-4。 In the method of manufacturing a liquid crystal display device of the seventh embodiment, the liquid crystal display device includes a liquid crystal layer including liquid crystal molecules having negative dielectric anisotropy, and the irradiation direction in the polarized light irradiation step is different, and the implementation is performed in addition to the above. The manufacturing method of the liquid crystal display device of Example 1 was the same. The dielectric constant of the liquid crystal material used was -4.

(偏光照射步驟) (polarized illumination step)

對TFT基板及CF基板上之正式焙燒步驟後之膜自法線方向照射直線偏光紫外線。直線偏光紫外線之照射量係於中心波長313nm附近設為30mJ/cm2。 再者，於實施例7中，於TFT基板中，以偏光照射方向與FFS模式用之電極之狹縫方向大致平行之方式照射直線偏光紫外線。 The film after the main baking step on the TFT substrate and the CF substrate is irradiated with linearly polarized ultraviolet rays from the normal direction. The amount of irradiation of the linearly polarized ultraviolet rays was set to 30 mJ/cm 2 in the vicinity of the center wavelength of 313 nm. Further, in the seventh embodiment, the linearly polarized ultraviolet ray is irradiated on the TFT substrate so that the direction in which the polarized light is irradiated is substantially parallel to the slit direction of the electrode for the FFS mode.

對藉由實施例7之液晶顯示裝置之製造方法所製造之液晶顯示裝置評價對比度。對比度之測定係藉由上述方法進行。實施例7中之對比度為1600，為進一步高於實施例1之值。 The contrast was evaluated on the liquid crystal display device manufactured by the method for producing a liquid crystal display device of Example 7. The measurement of contrast is carried out by the above method. The contrast ratio in Example 7 was 1600, which was further higher than the value of Example 1.

關於實施例8-1之液晶顯示裝置之製造方法，光反應性聚合物與非光反應性聚合物之調配比不同，除該方面以外，與實施例1之液晶顯示裝置之製造方法相同。於實施例8-1中，光反應性聚合物與非光反應性聚合物之調配比設為10：90。即，相對於光配向膜材料所含有之固形物成分整體，光反應性聚合物之比率為10重量%，非光反應性聚合物之比率為90重量%。 The method for producing a liquid crystal display device of Example 8-1 is the same as the method for producing a liquid crystal display device of Example 1, except that the ratio of the photoreactive polymer to the non-photoreactive polymer is different. In Example 8-1, the compounding ratio of the photoreactive polymer to the non-photoreactive polymer was set to 10:90. That is, the ratio of the photoreactive polymer to the entire solid content component contained in the photo-alignment film material was 10% by weight, and the ratio of the non-photoreactive polymer was 90% by weight.

關於實施例8-2之液晶顯示裝置之製造方法，光反應性聚合物與非光反應性聚合物之調配比不同，除該方面以外，與實施例1之液晶顯示裝置之製造方法相同。於實施例8-2中，光反應性聚合物與非光反應性聚合物之調配比設為5：95。即，相對於光配向膜材料所含有之固形物成分整體，光反應性聚合物之比率為5重量%，非光反應性聚合物之比率為95重量%。 The method for producing a liquid crystal display device of Example 8-2 is the same as the method for producing a liquid crystal display device of Example 1, except that the ratio of the photoreactive polymer to the non-photoreactive polymer is different. In Example 8-2, the compounding ratio of the photoreactive polymer to the non-photoreactive polymer was set to 5:95. That is, the ratio of the photoreactive polymer to the entire solid content component contained in the photo-alignment film material was 5% by weight, and the ratio of the non-photoreactive polymer was 95% by weight.

關於實施例8-3之液晶顯示裝置之製造方法，光反應性聚合物與非光反應性聚合物之調配比不同，除該方面以外，與實施例1之液晶顯示裝置之製造方法相同。於實施例8-3中，光反應性聚合物與非光反應性聚合物之調配比設為50：50。即，相對於光配向膜材料所含有之固形物成分整體，光反應性聚合物之比率為50重量%，非光反應性聚合物之比率為50重量%。 The method for producing a liquid crystal display device of Example 8-3 is the same as the method for producing a liquid crystal display device of Example 1, except that the ratio of the photoreactive polymer to the non-photoreactive polymer is different. In Example 8-3, the compounding ratio of the photoreactive polymer to the non-photoreactive polymer was set to 50:50. That is, the ratio of the photoreactive polymer to the entire solid content component contained in the photo-alignment film material was 50% by weight, and the ratio of the non-photoreactive polymer was 50% by weight.

關於實施例8-4之液晶顯示裝置之製造方法，光反應性聚合物與非光反應性聚合物之調配比不同，除該方面以外，與實施例1之液晶顯示裝置之製造方法相同。於實施例8-4中，光反應性聚合物與非光反應性聚合物之調配比設為2.5：97.5。即，相對於光配向膜材料所含有之固形物成分整體，光反應性聚合物之比率為2.5重量%，非光反應性聚合物之比率為97.5重量%。 The method for producing a liquid crystal display device of Example 8-4 is the same as the method for producing a liquid crystal display device of Example 1, except that the ratio of the photoreactive polymer to the non-photoreactive polymer is different. In Example 8-4, the compounding ratio of the photoreactive polymer to the non-photoreactive polymer was set to 2.5:97.5. That is, the ratio of the photoreactive polymer to the entire solid content component contained in the photo-alignment film material was 2.5% by weight, and the ratio of the non-photoreactive polymer was 97.5% by weight.

對藉由實施例1、實施例8-1~8-4之液晶顯示裝置之製造方法所製造之液晶顯示裝置評價對比度及電壓保持率(VHR)。對比度及VHR之測定係藉由上述方法進行。將評價結果示於下述表6。 The contrast and voltage holding ratio (VHR) of the liquid crystal display device manufactured by the method for manufacturing a liquid crystal display device of Example 1 and Examples 8-1 to 8-4 were evaluated. The measurement of contrast and VHR was carried out by the above method. The evaluation results are shown in Table 6 below.

如表6所示，於實施例1、實施例8-1~8-4中，即便改變光反應性聚合物與非光反應性聚合物之調配比，亦成功獲得良好之對比度。進而，於使非光反應性聚合物之比率高於實施例1之實施例8-1、8-2及8-4中，VHR高於實施例1。另一方面，於使非光反應性聚合物之比率低於實施例1之實施例8-3中，VHR稍低於實施例1。作為VHR發生變化之原因，認為係以下之原因。藉由以兩個階段進行正式焙燒步驟，可促進光反應性聚合物與非光反應性聚合物之層分離。其結果為，即便光反應性聚合物之調配量較少，亦可於配向膜表面(配向膜之液晶層側)充分地使光反應性聚合物露出。藉由減少光反應性聚合物之調配量，可 增加對電氣特性改善有效果之非光反應性聚合物之調配量，故而認為可提供可靠性更高之液晶顯示裝置。 As shown in Table 6, in Example 1, Examples 8-1 to 8-4, even if the blending ratio of the photoreactive polymer to the non-photoreactive polymer was changed, a good contrast was successfully obtained. Further, in the case where the ratio of the non-photoreactive polymer was higher than that of Examples 8-1, 8-2 and 8-4 of Example 1, the VHR was higher than that of Example 1. On the other hand, in the case where the ratio of the non-photoreactive polymer was lower than that of Example 8-3 of Example 1, the VHR was slightly lower than that of Example 1. The reason for the change in VHR is considered to be the following reason. The layer separation of the photoreactive polymer and the non-photoreactive polymer can be promoted by performing the main calcination step in two stages. As a result, even if the amount of the photoreactive polymer is small, the photoreactive polymer can be sufficiently exposed on the surface of the alignment film (on the liquid crystal layer side of the alignment film). By reducing the amount of photoreactive polymer, It is considered that a liquid crystal display device having higher reliability can be provided by increasing the amount of non-photoreactive polymer which is effective for improving electrical characteristics.

上述各實施例係關於FFS模式之液晶顯示裝置之製造方法之情形，但可知即便為關於IPS模式之液晶顯示裝置之製造方法之情形，亦發揮本發明之一態樣之效果。 Each of the above embodiments relates to the method of manufacturing the liquid crystal display device of the FFS mode. However, it is understood that the effect of one aspect of the present invention is exhibited even in the case of the method of manufacturing the liquid crystal display device of the IPS mode.

再者，本發明之各實施例中記載之技術特徵可相互組合而形成新穎之本發明之實施態樣。 Furthermore, the technical features described in the various embodiments of the present invention can be combined with each other to form a novel embodiment of the present invention.

本發明之一態樣係具備光配向膜之液晶顯示裝置之製造方法，其依序包括：步驟(1)，其於基板上形成含有2種以上之聚合物及溶劑之光配向膜材料之膜；步驟(2)，其對上述膜進行使上述溶劑蒸發之預焙燒；步驟(3)，其對預焙燒後之上述膜自低溫至高溫於複數個溫度下階段性地進行正式焙燒；及步驟(4)，其對正式焙燒後之上述膜進行偏光照射；並且上述2種以上之聚合物中之至少一者可為側鏈具有光官能基之光反應性聚合物。根據上述態樣，藉由自低溫至高溫於複數個溫度下階段性地進行正式焙燒步驟，可促進配向膜中之光反應性聚合物與其他聚合物之層分離，於配向膜表面使光反應性聚合物露出。因此，於正式焙燒步驟後之偏光照射步驟中，即便藉由較小之偏光照射量亦可獲得對比度良好之液晶顯示裝置。又，由於在正式焙燒步驟後進行偏光照射步驟，故而聚合物不會伴隨有自組裝，可使配向膜之相位差較小。 An aspect of the present invention provides a method for producing a liquid crystal display device comprising a photo-alignment film, comprising: in step (1), a film for forming a photo-alignment film material containing two or more kinds of polymers and solvents on a substrate; a step (2) of pre-baking the film to evaporate the solvent; and a step (3) of periodically calcining the film after pre-baking from a low temperature to a high temperature at a plurality of temperatures; and a step (4) A polarizing irradiation of the film after the main baking is performed; and at least one of the two or more types of polymers may be a photoreactive polymer having a photofunctional group in a side chain. According to the above aspect, the step of performing the main calcination step at a plurality of temperatures from a low temperature to a high temperature can promote separation of the photoreactive polymer from the other polymer in the alignment film, and light reaction on the surface of the alignment film. The polymer is exposed. Therefore, in the polarized light irradiation step after the main baking step, a liquid crystal display device having a good contrast can be obtained even with a small amount of polarized light irradiation. Further, since the polarizing irradiation step is performed after the main baking step, the polymer is not accompanied by self-assembly, and the phase difference of the alignment film can be made small.

於上述態樣中，就有效率地進行上述溶劑之揮發之觀點而言，上述步驟(2)之預焙燒可於50℃以上且80℃以下之溫度下進行。於預焙燒之溫度未達50℃之情形時，上述溶劑之揮發需要時間，故而明顯產生伴隨溶液之對流之膜厚不均，其結果為，可能會於點亮液晶顯示裝置時視認到配向不均。於預焙燒之溫度超過80℃之情形時，溶劑之揮發急遽進行，配向膜中之光反應性聚合物與 其他聚合物無法形成良好之層分離狀態。因此，即便之後進行多階段之正式焙燒步驟，配向膜中之光反應性聚合物與其他聚合物之層分離亦可能會不充分。 「於50℃以上且80℃以下之溫度下進行預焙燒」係指例如以具有溫度為50℃以上且80℃以下之恆溫時間之方式進行預焙燒。50℃以上且80℃以下之恆溫時間可意指例如於±5℃之溫度範圍內保持30秒以上之加熱狀態之時間。關於上述步驟(2)之預焙燒，焙燒時間之較佳之下限為1分鐘，較佳之上限為10分鐘，更佳之下限為2分鐘，更佳之上限為5分鐘。 In the above aspect, the pre-baking of the above step (2) can be carried out at a temperature of from 50 ° C to 80 ° C from the viewpoint of efficiently volatilizing the solvent. When the pre-baking temperature is less than 50 ° C, the evaporation of the solvent takes time, so that the film thickness unevenness accompanying the convection of the solution is apparent, and as a result, the alignment may be recognized when the liquid crystal display device is lit. All. When the pre-baking temperature exceeds 80 ° C, the volatilization of the solvent proceeds rapidly, and the photoreactive polymer in the alignment film is Other polymers do not form a good layer separation state. Therefore, even if a multi-stage formal calcination step is carried out later, the separation of the photoreactive polymer in the alignment film from the layers of other polymers may be insufficient. "Pre-baking at a temperature of 50 ° C or more and 80 ° C or less" means pre-baking, for example, at a constant temperature of 50 ° C or more and 80 ° C or less. The constant temperature time of 50 ° C or more and 80 ° C or less may mean, for example, a time of maintaining a heating state of 30 seconds or more in a temperature range of ± 5 ° C. With respect to the pre-baking of the above step (2), the lower limit of the calcination time is preferably 1 minute, preferably 10 minutes, more preferably 2 minutes, and even more preferably 5 minutes.

於上述態樣中，上述步驟(3)之正式焙燒可包含於90℃以上且170℃以下之溫度下進行之第一階段。更佳為110℃以上且150℃以下。關於正式焙燒之第一階段，於低於進行聚醯胺酸之醯亞胺化之溫度之溫度下充分地進行加熱而使溶劑揮發較為重要。於配向膜材料中包含聚醯胺酸之情形時，例如N-甲基-2-吡咯啶酮(NMP)等高極性溶劑不易揮發，故而藉由多階段之正式焙燒而促進層分離尤其有效。關於上述步驟(3)之正式焙燒之第一階段，焙燒時間之較佳之下限為5分鐘，較佳之上限為60分鐘，更佳之下限為10分鐘，更佳之上限為30分鐘。 In the above aspect, the main calcination of the above step (3) may be carried out in the first stage at a temperature of 90 ° C or more and 170 ° C or less. More preferably, it is 110 ° C or more and 150 ° C or less. In the first stage of the main calcination, it is important to sufficiently heat the solvent at a temperature lower than the temperature at which the hydrazine imidization of the polyamic acid is carried out. When the poly-proline is contained in the alignment film material, for example, a highly polar solvent such as N-methyl-2-pyrrolidone (NMP) is not easily volatilized, so that it is particularly effective to promote layer separation by a plurality of stages of main baking. With regard to the first stage of the main calcination of the above step (3), the preferred lower limit of the calcination time is 5 minutes, preferably the upper limit is 60 minutes, more preferably the lower limit is 10 minutes, and even more preferably the upper limit is 30 minutes.

於上述態樣中，上述步驟(3)之正式焙燒可包含於200℃以上且240℃以下之溫度下進行之最終階段。藉由於200℃以上之高溫下進行正式焙燒之最終階段，可充分地推進聚醯胺酸之醯亞胺化，可使VHR進而良好。正式焙燒之最終階段之更佳之下限為220℃。關於上述步驟(3)之正式焙燒之最終階段，焙燒時間之較佳之下限為15分鐘，較佳之上限為90分鐘，更佳之下限為20分鐘，更佳之上限為60分鐘。 In the above aspect, the main calcination of the above step (3) may be carried out at a final stage of a temperature of 200 ° C or higher and 240 ° C or lower. By carrying out the final stage of the main calcination at a high temperature of 200 ° C or higher, the ruthenium imidization of the polyamine can be sufficiently promoted, and the VHR can be further improved. A preferred lower limit for the final stage of the final calcination is 220 °C. With regard to the final stage of the main calcination of the above step (3), the lower limit of the calcination time is preferably 15 minutes, preferably the upper limit is 90 minutes, more preferably the lower limit is 20 minutes, and even more preferably the upper limit is 60 minutes.

於上述態樣中，上述光官能基可為肉桂酸酯基。 In the above aspect, the above photofunctional group may be a cinnamate group.

於上述態樣中，上述光反應性聚合物可具有選自由聚矽氧烷、聚醯胺酸、聚醯亞胺及順丁烯二醯亞胺所組成之群中之至少1種結構。 In the above aspect, the photoreactive polymer may have at least one structure selected from the group consisting of polyoxyalkylene, polyglycolic acid, polyimine, and maleimide.

於上述態樣中，上述2種以上之聚合物可包含以聚醯胺酸及/或聚醯亞胺作為主鏈之非光反應性聚合物。 In the above aspect, the two or more polymers may include a non-photoreactive polymer having a polyamine and/or a polyimine as a main chain.

上述光反應性聚合物及上述非光反應性聚合物可使聚醯胺酸之一部分進行熱化學反應(熱醯亞胺化)，藉此，可進行光配向膜之比電阻或介電常數等電氣特性之調整。又，上述光反應性聚合物及上述非光反應性聚合物可為共聚物，藉由採用共聚物結構，可平衡性良好地調整光反應性之感度、電氣特性及配向特性。 The photoreactive polymer and the non-photoreactive polymer may be subjected to a thermochemical reaction (thermal imidization) of one of the polylysines, whereby the specific resistance or dielectric constant of the photoalignment film may be performed. Adjustment of electrical characteristics. Further, the photoreactive polymer and the non-photoreactive polymer may be copolymers, and by using a copolymer structure, the sensitivity, electrical properties, and alignment characteristics of photoreactivity can be adjusted with good balance.

於上述態樣中，上述光反應性聚合物之比率相對於上述光配向膜材料所含有之固形物成分整體可為5~30重量%。即便上述光反應性聚合物之比率為上述範圍，經過上述步驟(1)~(4)，藉此亦可於配向膜之液晶層側充分地使光反應性聚合物露出。又，藉由減少光反應性聚合物之調配量，可使對電氣特性改善有效果之上述非光反應性聚合物之比率較高，故而可使VHR進而良好。 In the above aspect, the ratio of the photoreactive polymer may be 5 to 30% by weight based on the total solid content of the photo-alignment film material. Even if the ratio of the photoreactive polymer is in the above range, the photoreactive polymer can be sufficiently exposed on the liquid crystal layer side of the alignment film by the above steps (1) to (4). Further, by reducing the amount of the photoreactive polymer, the ratio of the non-photoreactive polymer which is effective for improving electrical characteristics can be made high, so that the VHR can be further improved.

於上述態樣中，上述非光反應性聚合物之比率相對於上述光配向膜材料所含有之固形物成分整體可為70~95重量%。上述非光反應性聚合物由於對電氣特性改善有效果，故而藉由將上述非光反應性聚合物之比率設為上述範圍，可使VHR更良好。 In the above aspect, the ratio of the non-photoreactive polymer may be 70 to 95% by weight based on the total solid content of the photo-alignment film material. Since the non-photoreactive polymer is effective in improving electrical characteristics, the VHR can be further improved by setting the ratio of the non-photoreactive polymer to the above range.

於上述態樣中，於上述步驟(4)後，可包含於上述膜上形成配向維持層之步驟。藉由於上述膜上形成配向維持層，可使殘像特性優異。 In the above aspect, after the step (4), the step of forming the alignment maintaining layer on the film may be included. By forming the alignment maintaining layer on the film, the afterimage characteristics are excellent.

於上述態樣中，上述液晶顯示裝置可具備包含具有負介電常數各向異性之液晶分子之液晶層。藉由液晶層包含具有負介電常數各向異性之液晶分子，可獲得對比度更優異之液晶顯示裝置。 In the above aspect, the liquid crystal display device may include a liquid crystal layer including liquid crystal molecules having negative dielectric anisotropy. When the liquid crystal layer contains liquid crystal molecules having negative dielectric anisotropy, a liquid crystal display device having more excellent contrast can be obtained.

Claims (9)

一種液晶顯示裝置之製造方法，其特徵在於：其係具備光配向膜之液晶顯示裝置之製造方法，且依序包括：步驟(1)，其於基板上形成含有2種以上之聚合物及溶劑之光配向膜材料之膜；步驟(2)，其對上述膜進行使上述溶劑蒸發之預焙燒；步驟(3)，其對預焙燒後之上述膜自低溫至高溫於複數個溫度下階段性地進行正式焙燒；及步驟(4)，其對正式焙燒後之上述膜進行偏光照射；並且上述2種以上之聚合物中之至少一者為側鏈具有光官能基之光反應性聚合物，上述步驟(2)之預焙燒係於50℃以上且80℃以下之溫度下進行，上述步驟(3)之正式焙燒包括於90℃以上且170℃以下之溫度下進行之第一階段。 A method of manufacturing a liquid crystal display device, comprising: a method for producing a liquid crystal display device comprising a photoalignment film, and comprising: step (1) comprising forming two or more polymers and a solvent on a substrate a film of the light alignment film material; a step (2) of pre-baking the film to evaporate the solvent; and a step (3) of the film after pre-baking from a low temperature to a high temperature at a plurality of temperatures Formal calcination; and step (4), wherein the film after the main calcination is polarized; and at least one of the two or more polymers is a photoreactive polymer having a photofunctional group in a side chain, The pre-baking in the above step (2) is carried out at a temperature of 50 ° C or more and 80 ° C or less, and the main calcination of the above step (3) includes the first stage of the temperature of 90 ° C or more and 170 ° C or less. 如請求項1之液晶顯示裝置之製造方法，其中上述步驟(3)之正式焙燒包括於200℃以上且240℃以下之溫度下進行之最終階段。 The method of manufacturing a liquid crystal display device according to claim 1, wherein the main baking of the above step (3) comprises a final stage of performing at a temperature of 200 ° C or more and 240 ° C or less. 如請求項1或2項之液晶顯示裝置之製造方法，其中上述光官能基為肉桂酸酯基。 The method of producing a liquid crystal display device of claim 1 or 2, wherein the photofunctional group is a cinnamate group. 如請求項1或2項之液晶顯示裝置之製造方法，其中上述光反應性聚合物具有選自由聚矽氧烷、聚醯胺酸、聚醯亞胺及順丁烯二醯亞胺所組成之群中之至少1種結構。 The method of manufacturing a liquid crystal display device according to claim 1 or 2, wherein the photoreactive polymer has a polymer selected from the group consisting of polyoxyalkylene, polylysine, polyimine, and maleimide. At least one structure in the group. 如請求項1或2項之液晶顯示裝置之製造方法，其中上述2種以上之聚合物包含以聚醯胺酸及/或聚醯亞胺作為主鏈之非光反應性聚合物。 The method for producing a liquid crystal display device according to claim 1 or 2, wherein the two or more polymers include a non-photoreactive polymer having a polyamine and/or a polyimine as a main chain. 如請求項1或2項之液晶顯示裝置之製造方法，其中上述光反應性聚合物之比率相對於上述光配向膜材料所含有之固形物成分整體為5~30重量%。 The method of producing a liquid crystal display device according to claim 1 or 2, wherein the ratio of the photoreactive polymer is 5 to 30% by weight based on the total solid content of the photo-alignment film material. 如請求項5之液晶顯示裝置之製造方法，其中上述非光反應性聚合物之比率相對於上述光配向膜材料所含有之固形物成分整體為70~95重量%。 The method of producing a liquid crystal display device according to claim 5, wherein the ratio of the non-photoreactive polymer is 70 to 95% by weight based on the total solid content of the photo-alignment film material. 如請求項1或2項之液晶顯示裝置之製造方法，其於上述步驟(4)後，包括於上述膜上形成配向維持層之步驟。 A method of manufacturing a liquid crystal display device according to claim 1 or 2, comprising the step of forming an alignment maintaining layer on the film after the step (4). 如請求項1或2項之液晶顯示裝置之製造方法，其中上述液晶顯示裝置具備包含具有負介電常數各向異性之液晶分子之液晶層。 The method of manufacturing a liquid crystal display device according to claim 1 or 2, wherein the liquid crystal display device comprises a liquid crystal layer containing liquid crystal molecules having negative dielectric anisotropy.
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